Production of organic compounds



Patented Aug. 2, 1927.

UNITED STATES PATENT. OFFICE.

KARI: FRIEDRICH SCHMIDT, OF HEIDELBERG, AND PHILIP? ZUTAVEBN, O! LUDWIGS- HAFEN-ON-TIIE-BHINE, GERMANY, ASSIGNORS T0 KNOLL 8a CO., 0] LUDWIGB- HAIEN-ON-THE-BHINE, GERMANY, A FIRM COMPOSED OF ALBERT KNOLL, mus

KNOLL, AND MAX DAEGE.

PRODUCTION OI ORGANIC COMPOUNDS.

Io Drawing. Application filed December 11, 1925, Serial No. 74,885, and in Germany April 11, 1925.

nitrocompounds and in some cases by the use of phenols whereby the characteristic groups of the compounds are modified and/or exchanged.

The term, amines includes the primary amines, the secondary--amines and the ter- (-See A Text Book of Organic Chemistry, Richter, translated by Smith, volume 1, pages 166 and 167, P. Blakistons Son & Company, 1913). The

tiary amines.

present invention resides in the broad process of directly introducing either the NH, group, the NH responding to at present in the tertiary amines or their derivatives into hydrocarbons carbonyl compounds and derivatives of these bodies. Under the expression carbonyl compounds we include such comsounds as contain at least one -ketoor alehyde group. 1 I The expression trivalent basic nitrogen,

as hereinafter used, isthe generic expression for amino-nitrogen whether one, two or three of the valences of the nitrogen are satisfied by hydrogen atoms i. e. whether such nitrogen occurs in primary, secondary or tertiary amines and it is also intended to include the nitrogen in the nitriles (-G=N). It is not necessary that the final product have basic properties.

The concentrated mineral acids are exam les of one type of, catalyst which will facllitate the direct introduction of the amino nitrogen into the hydrocarbon comunds or their derivatives. Other cata lyt'c agents as hereinafter more specifically set forth have been found to give very satisfactory results. It is to be understood that the present invention is broadly directed to the use of any catalyst which will facilitate roup or amino nitrogen cort.

basic properties which destroy the hydrazoic acid by neutralization. Besides inorganic catalysts, it has also been discovered that organic catalysts, such as sulphoacetic acid SO,HCH,.COOH and ethyl sulphuric acid may be used. A gaseous substance as gaseous hydrochloric acid may also be used as a catalyzer in the place of sulphuric acid or the above catalyzers. When the above catalysts are used instead of sulphuric acid they are added to the reaction mixture until the evolution of gas ceases.

Using concentrated mineral acid or any of the above named catalysts either in molecular proportions or in excess, the processes are as a rule. carried out without danger and with good yields, when working with small quantities, that is, on the laboratory scale, provided sufiicient precautions are observed. However, great difiiculties are encountered in transferring the process from a laboratory scale to commercial operation. On operating with large quantities of the reacting materials, the reactions proceed with great violence and with very great evolution of heat and, in view of the explosiveness of the hydrazoic acid, series accidents may be caused and the yield may be greatly reduced.

By using a nonacid inorganic catalyst it is possible to conduct the reactions so that the latter proceed quietly and uniformly and in addition, the ylelds, in many cases are greater than when the process is carried out by the use of concentrated mineral acid. The quantity'of the catalyst to be used will be determined by the process itself, as the tilling addition of the contact substance must be continued until the calculated amount of nitrogen is evolved.

As specific examples of the manner of practicing the above processes, the following are given:

Ewample 1.

200 parts benzol solution of hydrazoic acid containing 30 parts N H were gradually mixed with anhydrous A101 while cooled until the evolution of gas ceased. With the addition of ice it was made alkaline with caustic soda solution and the resulting aniline was carried over by steam.

Example 2.

3 mol. dimethyl acetoacetic ester, dissolved in 1300 cc. benzol solution of hydrazoic acid containing 4 mol. N H were dropped while cooled on 1 kg. of anhydrous iron chloride. After the end of the evolution of gas (65 liters N it was made alkaline with caustic soda solution, extracted with benzol and the benzol distilled off. Residue, acetylamidoisobutyric acid ester.

Example 3.

260 parts benzaldehyde dissolved in 1000 parts benzol nitride with a content of H parts N H were treated with dried hydrochloric acid gas whileconstantly agitated until no gas evolution followed. After disofi the benzol benzonitrile remained behind.

CHs-OHs-OH-OOOCaHu+ O dJHr-U O a 5 Example 5.

49 of cyclohexanon are dissolved in 200 cc. 0. benzol, either or tetralin containing 21.5 g. hydrazoic acid and while well cooling 30 g. of thionyl chlorid are added drop by rop.

The yield of leucinlactam is about 40 P The reaction probably takes place as follows Ewample 4.

170 arts cyclohexanone carboxylic acid ester dissolved in 1000 parts benzol solution of hydrazoic acid containing 60 parts N H were treated with dried hydrochloric acid gas during agitation and constantcooling until the evolution of nitrogen ceased. The resulting mixture was agitated with water, the water layer drawn oif from the benzol, heated for 3 hours to boiling under a reflux and then boiled down in vacuum to crystaliization. The hydrochloric acid salt of the amidopimelic acid crystallized out.

, NH, om-om-hn-ooon tent compounds. Those compounds above which contain keto or aldehyde groups are specifically covered in the claims by the expression carbonyl compounds.

We claim 1. The process of treating organic comounds of, the hydrocarbon t e to directly Introduce therein trivalent asic nitrogen comprising adding thereto hydrazoic acid in the presence of a catalyst.

2. The process of treating organic compounds of the hydrocarbon type to directly introduce therein trivalent basic nitro 11 comprising adding thereto hydrazolc aci in the presence of an inorganic catalyst.

3. The process of treating organic com-' pounds of the hydrocarbon type to directly I introduce therein trivalent basic nitrogen comprising adding thereto hydrazoic acid in the presence of inorganic catalysts which are not mineral acids but are salts and other compounds.

4. The process of treating organic compounds of the hydrocarbon type to directly introduce therein trivalent basic nitro en comprising adding thereto hydrazoic aci in the presence of a catalyst consisting of an inorganic chlorid.

5. The process of treating organic comea-mar tetrachloride, potassium chlostannate, am-j monium chlorstannate, antimony trichloride, aluminum chloride, hyrochloric acid and their equivalents.

6. The process of making derivatives of hgdrazoic amines including the imines and eir substitution products comprising treating organic compounds of the hydrocarbon type with inorganic catalysts which are not mineral acids but are salts and other compounds in the presence of hydrazoic acid.

7. The process of treating carbonyl comounds to directly introduce therein trivaent amino nitrogen comprising adding thereto hydrazoic acid in the presence of a catalgskt;

8. e process of treating carbonyl comunds to directly introduce therein trivaent amino nitrogen comprising adding thereto hydrazoic acid in the presence of an inorganic catalyst. v

9. The process of treating carbonyl compounds to directly introduce therein trivalent amino nitrogen comprising adding thereto hydrazoic acid in the presence of inorganic catalysts which are not mineral acids but are salts and other compounds.

pentachloride, ph oss 10. The process of treating carbonyl compounds to directly introduce the-rein trivalent amino' nitrogen comprising adding thereto hydrazoic acid in the presence of a catalyst consistingof an inorganic chlorid.

11. The process of treating carbonyl comounds to directly introduce therein trivaent amino nitrogen comprising adding thereto hydrazoic acid in the presence of a catalyst comprising oneof the following group: zinc chloride, iron chloride, phosphorus pentachloride, phos horns trichloride, phosphorus oxychlori e, phosphorus pentoxi'd, tin dichloride, potassium chlorstannate, stannate, antimony trichloride, ric acid and their e uivalents.

12. The process 0 treating organic compounds of the hydrocarbon type to directly introduce therein trivalent amino nitrogen comprising adding thereto hydrazoic acid in the resence of a catalyst which will not neutralize the acid.

13. The process of treating carbonyl compounds to directly introduce therein trivalent amino nitrogen comprising adding thereto hydrazoic acid in the presence of a catalyst which will not neutralize the acid.

In testimony that the foregoing we claim as our invention, we have slgned our names hereto.

KARL FRIEDRICH SCHMIDT. PHILIP]? ZUTAVERN.

ammonium chlorhydrochlo' tin tetrachloride, 

